KR102476584B1 - Composition for thermally conductive sheet and thermally conductive sheet prepared therefrom - Google Patents
Composition for thermally conductive sheet and thermally conductive sheet prepared therefrom Download PDFInfo
- Publication number
- KR102476584B1 KR102476584B1 KR1020190082964A KR20190082964A KR102476584B1 KR 102476584 B1 KR102476584 B1 KR 102476584B1 KR 1020190082964 A KR1020190082964 A KR 1020190082964A KR 20190082964 A KR20190082964 A KR 20190082964A KR 102476584 B1 KR102476584 B1 KR 102476584B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- thermally conductive
- acrylate
- conductive sheet
- composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 56
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011231 conductive filler Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 16
- -1 2-ethylhexyl Chemical group 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000009413 insulation Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 230000017525 heat dissipation Effects 0.000 description 8
- 239000004020 conductor Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 206010014357 Electric shock Diseases 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 102220043159 rs587780996 Human genes 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F20/10—Esters
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- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
본 발명은 열전도성 및 절연특성이 우수하고 취급이 용이한 열전도성 시트용 조성물 및 그로부터 제조된 열전도성 시트를 제공한다. 본 발명의 일 구현예에 따른 열전도성 시트용 조성물은 열전도성 충전제, 가소제, 아크릴산 및 알킬 (메타)아크릴레이트를 포함한다. The present invention provides a composition for a thermally conductive sheet having excellent thermal conductivity and insulating properties and easy handling, and a thermally conductive sheet prepared therefrom. A composition for a thermally conductive sheet according to an embodiment of the present invention includes a thermally conductive filler, a plasticizer, acrylic acid and an alkyl (meth)acrylate.
Description
본 발명은 열전도성 시트용 조성물 및 그로부터 제조된 열전도성 시트에 관한 것이다. 구체적으로, 본 발명은 절연특성이 우수한 열전도성 시트용 조성물 및 그로부터 제조된 열전도성 시트에 관한 것이다. The present invention relates to a composition for a thermally conductive sheet and a thermally conductive sheet prepared therefrom. Specifically, the present invention relates to a composition for a thermally conductive sheet having excellent insulating properties and a thermally conductive sheet prepared therefrom.
최근, 전자 기기의 고출력화에 따른 발열 밀도의 증가에 의해, 방열 대책의 중요성이 높아지고 있다. 특히 전기차에 대한 수요가 증가하면서, 전기차에 장착되는 고용량 배터리의 고효율 방열을 위한 수단이 필요하다.BACKGROUND OF THE INVENTION [0002] In recent years, the importance of countermeasures against heat dissipation has increased due to an increase in heat generation density associated with higher output of electronic devices. In particular, as the demand for electric vehicles increases, means for high-efficiency heat dissipation of high-capacity batteries installed in electric vehicles are required.
배터리의 과열에 의한 열적 트러블을 경감하기 위해서는, 주변 부재에 악영향을 미치지 않도록 기기 내에서 발생한 열을 신속하게 냉각재나 하우징 등의 방열체로 빼내는 것이 중요하며, 알루미늄, 구리 등의 금속제 방열체를 부착하는 것이 일반적이다. In order to alleviate thermal problems caused by overheating of the battery, it is important to quickly remove the heat generated in the device through a cooling material or a radiator such as a housing so as not to adversely affect the surrounding members. it is common
그러나, 이러한 방열체와 전자 기기 사이의 효율적인 열 방출 및 냉각을 위하여 방열부재가 반드시 필요하다. 방열 부재로는 일반적으로 열전도성 시트가 이용되고 있으며, 열전도성 시트는 기기 내부에서 발생된 열을 효율적으로 냉각 또는 방출하기 위해 히트 싱크(냉각 부재), 방열 시트, 냉각 플레이트 등을 전자 기기에 접합시키는 데 널리 사용되어 왔다. 따라서, 열전도성 시트는 높은 열전도도와 충분한 유연성을 가질 것이 요구된다. However, a heat dissipation member is absolutely necessary for efficient heat dissipation and cooling between the heat dissipating body and the electronic device. A thermal conductive sheet is generally used as a heat dissipation member, and the thermal conductive sheet is bonded to an electronic device such as a heat sink (cooling member), a heat dissipation sheet, a cooling plate, etc. to efficiently cool or dissipate heat generated inside the device. It has been widely used to make Therefore, the thermally conductive sheet is required to have high thermal conductivity and sufficient flexibility.
한편, 금속제 방열체를 부착하는 경우, 일반적으로 금속은 도전성이 있기 때문에, 냉각재나 하우징으로의 누전에 의한 문제점을 막기 위해, 많은 경우에 있어서 방열부재에는 전기 절연성도 요구된다. On the other hand, when attaching a metal radiator, since metal is generally conductive, electrical insulation is also required for the heat dissipation member in many cases in order to prevent problems caused by electric leakage to the coolant or the housing.
그러나, 일반적인 열전도성 아크릴계 시트로는 고절연성을 달성하기에 한계가 있어, 열전도성 및 절연성이 우수한 새로운 구성의 열전도성 시트에 대한 개발이 필요한 실정이다. However, there is a limit to achieving high insulation with general thermally conductive acrylic sheets, and thus, there is a need to develop a new thermally conductive sheet having excellent thermal conductivity and insulating properties.
본 발명이 해결하고자 하는 기술적 과제는 열전도성, 절연특성 및 취급용이성이 우수한 열전도성 시트용 조성물 및 그로부터 제조된 열전도성 시트를 제공하는 것이다.A technical problem to be solved by the present invention is to provide a composition for a thermally conductive sheet having excellent thermal conductivity, insulating properties and ease of handling, and a thermally conductive sheet prepared therefrom.
본 발명의 일 측면에 따르면, 열전도성 충전제, 가소제, 아크릴산 및 알킬 (메타)아크릴레이트 단량체를 포함하는 열전도성 시트용 조성물로서, 상기 아크릴산은 상기 알킬 (메타)아크릴레이트 단량체 100 중량부에 대해 0.3 중량부 내지 0.5 중량부로 포함되는 열전도성 시트용 조성물을 제공한다.According to one aspect of the present invention, a composition for a thermally conductive sheet comprising a thermally conductive filler, a plasticizer, acrylic acid and an alkyl (meth)acrylate monomer, wherein the acrylic acid is 0.3 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate monomer It provides a composition for a thermally conductive sheet included in an amount of 0.5 parts by weight to 0.5 parts by weight.
본 발명의 다른 측면에 따르면, 상기 열전도성 시트용 조성물의 경화물을 포함하고, 표면 저항이 2*1013 Ω/□ 내지 6*1013 Ω/□ 인 열전도성 시트를 제공한다.According to another aspect of the present invention, a thermally conductive sheet comprising a cured product of the composition for a thermally conductive sheet and having a surface resistance of 2*10 13 Ω/□ to 6*10 13 Ω/□ is provided.
본 발명에 따른 열전도성 시트는 열전도성이 우수하여 배터리에 적용되었을 경우 방열 성능이 우수할 수 있고, 절연특성이 우수하여 배터리 과열에 의한 폭발 등의 문제 발생을 방지할 수 있으며, 경도가 낮아 롤 형태의 권취가 가능하고 이에 따른 취급이 용이할 수 있다. The thermal conductive sheet according to the present invention has excellent thermal conductivity, so when applied to a battery, it can have excellent heat dissipation performance, has excellent insulation properties, can prevent problems such as explosion due to overheating of the battery, and has low hardness It can be wound in a form and can be easily handled accordingly.
본 명세서에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In this specification, when a part is said to "include" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.
이하, 본 발명에 대하여 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 구현예에 따른 열전도성 시트용 조성물은 열전도성 충전제, 가소제, 아크릴산 및 알킬 (메타)아크릴레이트 단량체를 포함하는 열전도성 시트용 조성물로서, 상기 아크릴산은 상기 알킬 (메타)아크릴레이트 단량체 100 중량부에 대해 0.3 중량부 내지 0.5 중량부로 포함된다.A composition for a thermally conductive sheet according to an embodiment of the present invention is a composition for a thermally conductive sheet comprising a thermally conductive filler, a plasticizer, acrylic acid and an alkyl (meth)acrylate monomer, wherein the acrylic acid is the alkyl (meth)acrylate monomer It is included in 0.3 parts by weight to 0.5 parts by weight based on 100 parts by weight.
본 발명의 일 구현예에 따르면, 상기 열전도성 충전제는 생성된 열전도성 시트에서 높은 수준의 열전도도를 달성하기 위하여 사용될 수 있고, 열전도성 시트용 조성물 중에 균일하게 분산되어 사용될 수 있다. According to one embodiment of the present invention, the thermally conductive filler may be used to achieve a high level of thermal conductivity in the resulting thermally conductive sheet, and may be used while being uniformly dispersed in the thermally conductive sheet composition.
또한 상기 열전도성 충전제는 분말 또는 입자 형태로 사용될 수 있고, 입자의 형상은 다각형, 타원형, 구형, 바늘형, 평판형 또는 플레이크형 형상일 수 있다. In addition, the thermally conductive filler may be used in the form of powder or particles, and the shape of the particles may be polygonal, elliptical, spherical, needle, flat, or flake.
본 발명의 일 구현예에 따르면, 열전도성 충전제는 입자 크기를 2가지 이상으로 다르게 하여 사용할 수 있다. 구체적으로, 보다 큰 크기의 입자와 보다 작은 크기의 입자를 함께 사용할 수 있다. 큰 크기의 입자는 직경이 8 μm 내지 30μm 또는 10 μm 내지 20μm 일 수 있고, 작은 크기의 입자는 직경이 0.5 μm 내지 5 μm 또는 1.5 μm 내지 5 μm 일 수 있다. 큰 크기의 입자는 충전율을 높일 수 있으며, 공정성을 우수하게 하고, 작은 크기의 입자는 침강을 방지하는 효과가 있으며, 응집력을 향상시킬 수 있다. According to one embodiment of the present invention, the thermally conductive filler may be used with two or more different particle sizes. Specifically, larger-sized particles and smaller-sized particles may be used together. Large size particles may be 8 μm to 30 μm or 10 μm to 20 μm in diameter, and small size particles may be 0.5 μm to 5 μm or 1.5 μm to 5 μm in diameter. Large-sized particles can increase the filling rate and improve processability, and small-sized particles have the effect of preventing settling and improving cohesion.
본 발명의 일 구현예에 따르면, 상기 열전도성 충전제는 수산화알루미늄, 산화 알루미늄, 질화 붕소, 질화 알루미늄, 산화 마그네슘, 수산화 마그네슘, 탄산 마그네슘, 산화 티탄, 산화 아연, 탄화 규소 및 석영 중 1종 이상일 수 있다. 바람직하게는, 난연성과 경제성 측면에서 상기 열전도성 충전제로 수산화 알루미늄을 사용할 수 있다. According to one embodiment of the present invention, the thermally conductive filler may be at least one of aluminum hydroxide, aluminum oxide, boron nitride, aluminum nitride, magnesium oxide, magnesium hydroxide, magnesium carbonate, titanium oxide, zinc oxide, silicon carbide, and quartz. there is. Preferably, aluminum hydroxide may be used as the thermally conductive filler in terms of flame retardancy and economy.
본 발명의 일 구현예에 따르면, 상기 열전도성 충전제는 상기 알킬 (메타)아크릴레이트 100 중량부에 대하여 500 중량부 내지 1000 중량부, 600 중량부 내지 900 중량부 또는 700 중량부 내지 850 중량부로 포함될 수 있다. 상기 범위 내의 함량으로 열전도성 충전제를 포함하는 경우, 조성물의 경화물을 포함하는 열전도성 시트가 충분한 열전도도를 가질 수 있으며 유연성을 갖는 시트를 제조할 수 있다. According to one embodiment of the present invention, the thermally conductive filler is included in an amount of 500 parts by weight to 1000 parts by weight, 600 parts by weight to 900 parts by weight, or 700 parts by weight to 850 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate. can When the thermally conductive filler is included in an amount within the above range, a thermally conductive sheet including a cured product of the composition may have sufficient thermal conductivity and a flexible sheet may be manufactured.
본 발명의 일 구현예에 따르면, 상기 가소제는 열전도성 시트의 유연성을 향상시키기 위해 열전도성 시트용 조성물에 포함될 수 있다. According to one embodiment of the present invention, the plasticizer may be included in a composition for a thermally conductive sheet to improve flexibility of the thermally conductive sheet.
본 발명의 일 구현예에 따르면, 상기 가소제는 점도가 10 cp 내지 450 cp, 20 cp 내지 450 cp 또는 20 cp 내지 430 cp 일 수 있다. 상기 범위 내의 점도를 가지는 가소제를 사용하는 경우, 열전도성 시트용 조성물의 점도를 적절히 조절하여 시트를 제조하는 공정상 도포성이 우수할 수 있다. According to one embodiment of the present invention, the plasticizer may have a viscosity of 10 cp to 450 cp, 20 cp to 450 cp, or 20 cp to 430 cp. When a plasticizer having a viscosity within the above range is used, coating properties may be excellent in a process of manufacturing a sheet by appropriately adjusting the viscosity of the composition for a thermally conductive sheet.
본 발명의 일 구현예에 따르면, 상기 가소제는 트리에틸헥실 트리멜리테이트, 트리이소노닐 트리멜리테이트 및 디이소노닐 아디페이트 중 1종 이상일 수 있다. 바람직하게는, 상기 가소제는 디이소노닐 아디페이트일 수 있다. According to one embodiment of the present invention, the plasticizer may be at least one of triethylhexyl trimellitate, triisononyl trimellitate and diisononyl adipate. Preferably, the plasticizer may be diisononyl adipate.
본 발명의 일 구현예에 따르면, 상기 가소제는 비점이 200 ℃ 내지 450 ℃, 210 ℃ 내지 420 ℃ 또는 210 ℃ 내지 310 ℃일 수 있다. 가소제의 비점이 상기 범위 내인 경우, 열전도성 시트가 고온에 장시간 노출되더라도 가소제가 쉽게 증발하지 않아 시트의 경화를 방지할 수 있고, 이에 따라 접착 성능 및 열성능을 우수하게 유지할 수 있다. According to one embodiment of the present invention, the plasticizer may have a boiling point of 200 °C to 450 °C, 210 °C to 420 °C, or 210 °C to 310 °C. When the boiling point of the plasticizer is within the above range, even when the thermally conductive sheet is exposed to high temperatures for a long time, the plasticizer does not easily evaporate and hardening of the sheet can be prevented, and thus adhesive performance and thermal performance can be maintained excellently.
본 발명의 일 구현예에 따르면, 상기 가소제는 상기 알킬 (메타)아크릴레이트 단량체100 중량부에 대하여 30 중량부 내지 80 중량부, 40 중량부 내지 60 중량부 또는 40 중량부 내지 55 중량부로 포함될 수 있다. 상기 범위 내의 함량으로 가소제가 포함되는 경우, 열전도성 시트에 유연성은 충분히 부여하면서도 열전도성 시트용 조성물의 점도는 과도하게 감소시키지 않고, 장기간 저장시에도 가소제가 새어나오는 현상인 블리딩 현상의 발생을 방지할 수 있다.According to one embodiment of the present invention, the plasticizer may be included in 30 parts by weight to 80 parts by weight, 40 parts by weight to 60 parts by weight, or 40 parts by weight to 55 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate monomer there is. When the plasticizer is included in an amount within the above range, the viscosity of the thermally conductive sheet composition is not excessively reduced while sufficiently providing flexibility to the thermally conductive sheet, and the bleeding phenomenon, which is a phenomenon in which the plasticizer leaks out even during long-term storage, can be prevented. can
본 발명의 일 구현예에 따르면, 상기 아크릴산은 열전도성 시트용 조성물의 점도 감소를 최소화하면서도 열전도성 시트의 열전도성 및 유연성을 유지하고, 공정 안정성을 해치지 않으며 전기 절연성을 우수하게 하기 위해 열전도성 시트용 조성물에 첨가될 수 있다. According to one embodiment of the present invention, the acrylic acid is used to maintain the thermal conductivity and flexibility of the thermal conductive sheet while minimizing the decrease in viscosity of the thermal conductive sheet composition, and to improve electrical insulation without compromising process stability. It can be added to the composition for
본 발명의 일 구현예에 따르면, 상기 아크릴산은 상기 알킬 (메타)아크릴레이트 단량체 100 중량부에 대해 0.3 중량부 내지 0.5 중량부, 0.33 중량부 내지 0.5 중량부 또는 0.33 중량부 내지 0.4 중량부로 포함된다. 열전도성 시트용 조성물이 상기 범위 내의 아크릴산을 포함하는 경우, 열저항이 낮고 열전도도가 높으며, 표면저항이 높고 절연특성이 우수하며 유전율이 낮고 유지율은 높은 열전도성 시트를 제조할 수 있다. According to one embodiment of the present invention, The acrylic acid is included in 0.3 parts by weight to 0.5 parts by weight, 0.33 parts by weight to 0.5 parts by weight, or 0.33 parts by weight to 0.4 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate monomer. When the composition for a thermally conductive sheet contains acrylic acid within the above range, a thermally conductive sheet having low thermal resistance, high thermal conductivity, high surface resistance, excellent insulating properties, low dielectric constant and high retention rate can be manufactured.
본 발명의 일 구현예에 따르면, 상기 알킬 (메타)아크릴레이트 단량체는 열전도성 시트용 조성물에 첨가되어 바인더의 역할을 하는 것일 수 있다. 구체적으로, 열전도성 충전제 및 가소제 등의 열전도성 시트용 조성물 성분을 결합하기 위해 포함되는 것일 수 있다. According to one embodiment of the present invention, the alkyl (meth)acrylate monomer may be added to the thermally conductive sheet composition to serve as a binder. Specifically, it may be included to bind components of a composition for a thermally conductive sheet such as a thermally conductive filler and a plasticizer.
본 발명의 일 구현예에 따르면, 상기 알킬 (메타)아크릴레이트 단량체는 탄소수 1 내지 15 또는 탄소수 7 내지 15인 알킬 (메타)아크릴레이트를 포함할 수 있다. According to one embodiment of the present invention, the alkyl (meth) acrylate monomer may include an alkyl (meth) acrylate having 1 to 15 carbon atoms or 7 to 15 carbon atoms.
본 발명의 일 구현예에 따르면, 상기 알킬 (메타)아크릴레이트 단량체는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 네오펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, 옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트 및 테트라데실 (메타)아크릴레이트 중 1종 이상을 포함할 수 있다. 바람직하게는, 상기 알킬 (메타)아크릴레이트는 2-에틸헥실 (메타)아크릴레이트 일 수 있다. According to one embodiment of the present invention, the alkyl (meth) acrylate monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate )Acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, octyl (metha)acrylate ) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and tetradecyl (meth) acrylate. Preferably, the alkyl (meth)acrylate may be 2-ethylhexyl (meth)acrylate.
본 발명의 일 구현예에 따르면, 상기 알킬 (메타)아크릴레이트 단량체는 유리 전이 온도가 -100 ℃ 이상 0 ℃ 이하일 수 있고, 비점이 200 ℃ 이상 300 ℃ 이상일 수 있다. According to one embodiment of the present invention, the alkyl (meth)acrylate monomer may have a glass transition temperature of -100 °C or more and 0 °C or less, and a boiling point of 200 °C or more and 300 °C or more.
본 발명의 일 구현예에 따른 열전도성 시트용 조성물은 광경화성 조성물일 수 있고, 광개시제 및 광경화제를 포함할 수 있다. 광개시제는 광 조사시 광에 의해 라디칼을 생성하여 경화반응을 개시하며, 광경화제는 조성물을 경화시켜 경화물의 기계강도 및 안정성을 향상시키는 역할을 한다. The composition for a thermally conductive sheet according to one embodiment of the present invention may be a photocurable composition and may include a photoinitiator and a photocuring agent. The photoinitiator initiates a curing reaction by generating radicals when irradiated with light, and the photocuring agent serves to improve the mechanical strength and stability of the cured product by curing the composition.
본 발명의 일 구현예에 따른 열전도성 시트용 조성물은 커플링제, 항산화제, 금속 불활성화제, 난연제, 점착성 부여제(tackifier), 침전 억제제, 요변성제(thixotropic agent), 계면활성제, 소포제, 착색제 및 정전기 방지제중 1종 이상을 첨가제로 더 포함할 수 있다. A composition for a thermally conductive sheet according to an embodiment of the present invention includes a coupling agent, an antioxidant, a metal deactivator, a flame retardant, a tackifier, a precipitation inhibitor, a thixotropic agent, a surfactant, an antifoaming agent, a colorant, and One or more of the antistatic agents may be further included as an additive.
본 발명의 다른 구현예에 따른 열전도성 시트는 본 발명에 따른 열전도성 시트용 조성물의 경화물을 포함하고, 표면 저항이 2*1013 Ω/□ 내지 6*1013 Ω/□이다.A thermally conductive sheet according to another embodiment of the present invention includes a cured product of the composition for a thermally conductive sheet according to the present invention, and has a surface resistance of 2*10 13 Ω/□ to 6*10 13 Ω/□.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 본 발명에 따른 열전도성 시트용 조성물의 광경화물을 포함하는 것일 수 있다. 구체적으로, 본 발명에 따른 열전도성 시트용 조성물을 100 nm 내지 400 nm, 300 nm 내지 400 nm 또는 315 nm 내지 400 nm의 파장의 자외선 광원을 이용하여 5 mW/cm2 내지 7 mW/cm2 의 UV를 10분간 조사하여 경화시킨 광경화물을 포함하는 것일 수 있다. According to one embodiment of the present invention, the thermally conductive sheet may include a photocured material of the composition for a thermally conductive sheet according to the present invention. Specifically, the composition for a thermally conductive sheet according to the present invention is 5 mW/cm 2 to 7 mW/cm 2 using an ultraviolet light source having a wavelength of 100 nm to 400 nm, 300 nm to 400 nm, or 315 nm to 400 nm. It may include a photo-cured material cured by irradiating UV for 10 minutes.
본 발명의 일 구현예에 따르면 상기 열전도성 시트는 표면 저항이 2*1013 Ω/□ 내지 6*1013 Ω/□, 2*1013 Ω/□ 내지 5.5*1013 Ω/□ 또는 2*1013 Ω/□ 내지 5*1013 Ω/□ 일 수 있다. 상기 범위 내의 표면 저항을 갖는 열전도성 시트가 전기차용 배터리팩에 적용되는 경우, 감전 위험이 없어 차량 및 배터리를 보호할 수 있다.According to one embodiment of the present invention, the thermal conductive sheet has a surface resistance of 2*10 13 Ω/□ to 6*10 13 Ω/□, 2*10 13 Ω/□ to 5.5*10 13 Ω/□ or 2* It may be 10 13 Ω/□ to 5*10 13 Ω/□. When the thermally conductive sheet having a surface resistance within the above range is applied to a battery pack for an electric vehicle, the vehicle and battery can be protected without risk of electric shock.
본 발명의 일 구현예에 따르면 상기 열전도성 시트는 절연특성이 5800 kΩ 내지 6000 kΩ, 5800 kΩ 내지 6000 kΩ, 또는 5800 kΩ 내지 5950 kΩ일 수 있다. 구체적으로, 상기 절연특성은 전지 시스템에 상기 열전도성 시트를 접지된 보호도체와, 활성도체로서 배터리의 사이에 개재하고, 측정기의 양극 및 음극을 각각 보호도체 접지 회로 및 배터리의 충전부에 연결하고 40 초 내지 80 초간 300 V 내지 700 V의 직류 전압을 인가한 후에 측정한 열전도성 시트의 저항값으로 측정될 수 있다. 상기 범위 내의 절연특성을 갖는 열전도성 시트가 전기차용 배터리팩에 적용되는 경우, 감전 위험이 없어 차량 및 배터리를 보호할 수 있다.According to one embodiment of the present invention, the thermal conductive sheet may have insulating properties of 5800 kΩ to 6000 kΩ, 5800 kΩ to 6000 kΩ, or 5800 kΩ to 5950 kΩ. Specifically, the insulation characteristics are such that the thermal conductive sheet is interposed between a protective conductor grounded in the battery system and a battery as an active conductor, and the positive and negative electrodes of the meter are connected to the protective conductor grounding circuit and the charging part of the battery, respectively, and 40 It may be measured as a resistance value of the thermally conductive sheet measured after applying a DC voltage of 300 V to 700 V for a second to 80 seconds. When the thermal conductive sheet having insulation characteristics within the above range is applied to a battery pack for an electric vehicle, the vehicle and battery can be protected without risk of electric shock.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 쇼어 00 경도가 70 내지 80 일 수 있다. 상기 범위 내의 낮은 쇼어 00 경도를 가지는 경우, 롤 형태의 권취가 가능하여 취급이 용이할 수 있다. According to one embodiment of the present invention, the thermally conductive sheet may have a Shore 00 hardness of 70 to 80. When it has a low Shore 00 hardness within the above range, it can be wound in a roll form and can be easily handled.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 커패시턴스 값이 0.2 nF 미만 또는 0.18 nF 미만일 수 있다. 상기 커패시턴스 값은 전도성 기재 사이에 열전도성 시트를 개재하고, 전도성 기재에 U1250A 멀티미터(아질리언트 社)와 같은 측정 기기를 연결하여 측정한 정전용량 값일 수 있다. 상기 범위 내의 작은 커패시턴스 값을 가지는 경우, 열전도성 시트의 절연성이 우수하여 안정성이 높을 수 있다. According to one embodiment of the present invention, the thermal conductive sheet may have a capacitance value of less than 0.2 nF or less than 0.18 nF. The capacitance value may be a capacitance value measured by interposing a thermal conductive sheet between conductive substrates and connecting a measuring device such as a U1250A multimeter (Agilent Co.) to the conductive substrate. In the case of having a small capacitance value within the above range, the insulation of the thermal conductive sheet may be excellent and stability may be high.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 두께가 1.0 mm 내지 3.0 mm 또는 2.0 mm 내지 3.0 mm일 수 있다. 상기 범위 내의 두께를 가지는 열전도성 시트는 롤 형태의 권취가 가능하여 취급이 용이하고, 전기차용 배터리팩에 적용되는 경우 우수한 열전도성을 가질 수 있으며, 모듈과 냉각 플레이트 사이의 단차흡수성이 우수할 수 있다. According to one embodiment of the present invention, the thermally conductive sheet may have a thickness of 1.0 mm to 3.0 mm or 2.0 mm to 3.0 mm. The thermal conductive sheet having a thickness within the above range can be rolled in a roll form and is easy to handle, and when applied to a battery pack for an electric vehicle, it can have excellent thermal conductivity and can have excellent step absorption between a module and a cooling plate. have.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 주파수 1 KHz 에서의 유전율이 3 내지 4 또는 3.3 내지 3.6 일 수 있다. 유전율은 낮을수록 절연 특성이 우수하며, 열전도성 시트의 유전율이 상기 범위 내인 경우, 절연 특성이 우수하여 안정성이 높을 수 있다.According to one embodiment of the present invention, the thermal conductive sheet may have a permittivity of 3 to 4 or 3.3 to 3.6 at a frequency of 1 KHz. The lower the permittivity is, the better the insulation properties are, and when the dielectric constant of the thermal conductive sheet is within the above range, the insulation properties are excellent and the stability may be high.
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 유전유지율이 60 % 내지 75 %, 또는 60 % 내지 70 % 일 수 있다. 구체적으로, 극성 물질은 주파수가 증가함에 따라 유전율이 감소하게 되는 바, 주파수의 증가에도 불구하고 유전율이 잘 유지될수록, 즉 유전유지율이 높을 수록 사용 환경이 변화하더라도 절연 특성이 우수하게 유지될 수 있다. 유전유지율은 하기 식 1에 따라 계산되는 값일 수 있다. 열전도성 시트의 유전유지율이 상기 범위 내인 경우, 절연 특성이 우수하여 안정성이 높을 수 있다. According to one embodiment of the present invention, the thermally conductive sheet may have a dielectric retention of 60% to 75%, or 60% to 70%. Specifically, since the dielectric constant of polar materials decreases as the frequency increases, the better the dielectric constant is maintained despite the increase in frequency, that is, the higher the dielectric constant, the better the insulating properties can be maintained even if the use environment changes. . Dielectric retention may be a value calculated according to Equation 1 below. When the dielectric retention of the thermal conductive sheet is within the above range, insulation properties may be excellent and stability may be high.
[식 1][Equation 1]
유전유지율(%) = 1 MHz 유전율 측정값 / 1 KHz 유전율 측정값 * 100Dielectric retention rate (%) = 1 MHz measured dielectric constant value / 1 KHz measured dielectric constant value * 100
본 발명의 일 구현예에 따르면, 상기 열전도성 시트는 열저항이 1.6 K-in2/W 내지 1.7 K-in2/W, 또는 1.65 K-in2/W 내지 1.7 K-in2/W 일 수 있고, 열전도도가 1.55 W/mK 내지 1.6 W/mK 일 수 있다. 상기 범위 내의 열저항 및 열전도도를 가지는 열전도성 시트의 경우, 열전도성이 우수하여 전기차용 배터리의 작동 중 발생하는 열을 효율적으로 배출할 수 있고, 이에 따라 전기차용 배터리의 과열 및 오작동 가능성을 낮추어 안정성이 우수할 수 있다. According to one embodiment of the present invention, the thermal conductive sheet has a thermal resistance of 1.6 K-in 2 /W to 1.7 K-in 2 /W, or 1.65 K-in 2 /W to 1.7 K-in 2 /W It may have a thermal conductivity of 1.55 W/mK to 1.6 W/mK. In the case of a thermal conductive sheet having thermal resistance and thermal conductivity within the above ranges, the thermal conductivity is excellent, so that the heat generated during operation of the electric vehicle battery can be efficiently discharged, thereby reducing the possibility of overheating and malfunction of the electric vehicle battery. Stability can be excellent.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 기술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to explain the present invention in detail. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present invention to those skilled in the art.
실시예 1Example 1
열전도성 충전제로 수산화알루미늄(오성기업 OSA-20, D50=20um, 순도 99.5% 이상 등) 500 g, 수산화알루미늄(Martinal OL-104LEO, D50=1.9um, 순도 99.5%이상) 130g, 2-에틸헥실(메타)아크릴레이트 100 g, 아크릴산 0.5 g, 커플링제(Borica, Tytan CP-318, Stearyl Titanate) 5g, 가소제로 디이소노닐 아디페이트(애경유화, 점도 20 cps, 비점 216℃) 50 g 및 경화제로는 1,6-헥산다이올다이아크릴레이트 0.35g, 광개시제로 Irgacure 651(BASF) 1 g을 혼합하고 교반하여 열전도성 시트용 조성물을 제조하였다. 열전도성 시트용 조성물을 PET 기재(오성산업, 75OS-UH02, 실리콘이형PET) 상에 도포하고 7 mW/cm2의 UV를 10분간 조사하고 광경화시켜 최종 두께가 2.0 mm 인 열전도성 시트를 제조하였다. As a thermally conductive filler, aluminum hydroxide (OSA-20, D50=20um, purity 99.5% or higher, etc.) 500 g, aluminum hydroxide (Martinal OL-104LEO, D50=1.9um, purity 99.5% or higher) 130g, 2-ethylhexyl 100 g of (meth)acrylate, 0.5 g of acrylic acid, 5 g of coupling agent (Borica, Tytan CP-318, Stearyl Titanate), 50 g of diisononyl adipate (Aekyung Petrochemical, viscosity 20 cps, boiling point 216 ° C) as a plasticizer and curing agent As a furnace, 0.35 g of 1,6-hexanediol diacrylate and 1 g of Irgacure 651 (BASF) as a photoinitiator were mixed and stirred to prepare a composition for a thermally conductive sheet. A thermal conductive sheet composition having a final thickness of 2.0 mm is prepared by applying a composition for a thermal conductive sheet onto a PET substrate (Ohsung Industry, 75OS-UH02, silicone release PET), irradiating 7 mW/cm 2 UV for 10 minutes, and photocuring the composition. did
실시예 2Example 2
아크릴산을 0.33 g 첨가한 것을 제외하고는 실시예 1 과 동일한 방법으로 열전도성 시트를 제조하였다. A thermally conductive sheet was prepared in the same manner as in Example 1, except that 0.33 g of acrylic acid was added.
비교예 1Comparative Example 1
아크릴산을 첨가하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 열전도성 시트를 제조하였다. A thermally conductive sheet was prepared in the same manner as in Example 1, except that acrylic acid was not added.
비교예 2Comparative Example 2
아크릴산을 1 g 첨가한 것을 제외하고는 실시예 1 과 동일한 방법으로 열전도성 시트를 제조하였다. A thermally conductive sheet was prepared in the same manner as in Example 1, except that 1 g of acrylic acid was added.
표면저항 및 절연특성의 측정Measurement of surface resistance and insulation properties
MCP-HT800 (미츠비시 케미컬 社)를 이용하여, 500 V의 전압을 60 초간 인가하여 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트의 표면 저항을 측정하였다. 표면 저항을 5회 측정한 후, 중간값 3개의 평균을 내어 표 1에 나타내었다. Using MCP-HT800 (Mitsubishi Chemical Co.), a voltage of 500 V was applied for 60 seconds to measure the surface resistance of the thermally conductive sheets prepared in Examples 1 and 2, Comparative Examples 1 and 2. After measuring the surface resistance 5 times, the average of the three intermediate values is shown in Table 1.
또한 파우치형 배터리셀을 이용하여 제조한 차량용 전지 시스템에 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트를 접지된 보호도체로서 냉각 플레이트(LT정밀 社)와, 활성도체로서 배터리(LG화학 社)의 사이에 개재하고, 측정기의 양극 및 음극을 각각 보호도체 접지 회로 및 상기 배터리의 충전부에 연결하고 60 초간 500 V 의 직류 전압을 인가하여 열전도성 시트의 저항값을 측정하여 절연 특성을 측정하였다. In addition, a cooling plate (LT Precision Co.) as a protective conductor grounded with the thermal conductive sheet prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 in the vehicle battery system manufactured using the pouch-type battery cell, As an active conductor, it is interposed between batteries (LG Chem), and the anode and cathode of the measuring instrument are connected to the protective conductor grounding circuit and the charging part of the battery, respectively, and a DC voltage of 500 V is applied for 60 seconds to determine the resistance value of the thermal conductive sheet. Insulation properties were measured by measuring.
커패시턴스의 측정Measurement of capacitance
실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트를 50 cm * 100 cm 로 재단하여 준비하고, SUS 304(재현상사)를 각각 70 cm * 100 cm 로 재단하여 2개를 준비하였다. 하부 SUS 기재 상에 열전도성 시트를 적층하고, 열전도성 시트 상에 상부 SUS 기재를 적층하여 적층체를 제조하였다. 상부 및 하부 SUS 기재를 각각 분해능이 0.001 nF인 멀티미터 U1250A (아질리언트 社)에 연결하여 커패시턴스를 측정하였다. 측정한 값은 표 1에 나타내었다. The thermal conductive sheets prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were prepared by cutting to 50 cm * 100 cm, and SUS 304 (re-developed yarn) was cut to 70 cm * 100 cm, respectively, and 2 prepared the dog. A laminate was prepared by laminating a thermal conductive sheet on the lower SUS substrate and laminating an upper SUS substrate on the thermal conductive sheet. Capacitance was measured by connecting the upper and lower SUS substrates to a multimeter U1250A (Agilent Co.) having a resolution of 0.001 nF, respectively. The measured values are shown in Table 1.
유전율 및 유지율의 측정Measurement of permittivity and retention
주파수 1 KHz 의 조건에서 E4980A (에이질런트 社) 및 정밀 LCR 미터기를 사용하여, 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트의 유전율을 측정하였다. 또한 주파수 1 MHz 의 조건에서 E4980A (에이질런트 社) 및 정밀 LCR 미터기를 사용하여 유전율을 측정한 후, 식 1에 따라 유지율을 계산하였다. 주파수 1 KHz 에서의 유전율 및 식 1에 따라 계산한 유전유지율 값을 표 1에 나타내었다. Permittivity of the thermally conductive sheets prepared in Examples 1, 2, Comparative Examples 1 and 2 was measured using E4980A (Agilent Co.) and a precision LCR meter under the condition of a frequency of 1 KHz. In addition, the dielectric constant was measured using E4980A (Agilent Co.) and a precision LCR meter under the condition of a frequency of 1 MHz, and then the retention factor was calculated according to Equation 1. The dielectric constant at a frequency of 1 KHz and the dielectric retention value calculated according to Equation 1 are shown in Table 1.
열저항 및 열전도도의 측정Measurement of thermal resistance and thermal conductivity
40 psi 조건에서 TIM Tester 1300 (어낼러시스 테크 社)를 이용하여 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트의 열저항 및 열전도도를 측정하였고, 이를 표 1에 나타내었다. Thermal resistance and thermal conductivity of the thermally conductive sheets prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were measured using a TIM Tester 1300 (Analysis Tech Co.) under a condition of 40 psi, which are shown in Table 1.
경도의 측정measurement of hardness
ASTM D2240 규격 HD3000, OS-00 모델 (힐데브랜드 社)을 이용하여 6T 샘플(400g 하중)로 30초간 하중을 주어 도출된 아날로그 값으로 실시예 1, 실시예 2, 비교예 1 및 비교예 2에서 제조한 열전도성 시트의 쇼어 00 경도를 측정하였다. 측정한 경도는 표 1에 나타내었다. In Example 1, Example 2, Comparative Example 1 and Comparative Example 2 as an analog value derived by applying a load for 30 seconds with a 6T sample (400g load) using the ASTM D2240 standard HD3000, OS-00 model (Hildebrand) Shore 00 hardness of the prepared thermal conductive sheet was measured. The measured hardness is shown in Table 1.
상기 표 1을 참조하면, 실시예 1 및 실시예 2의 경우 표면저항이 높고 절연특성이 5800 kΩ 이상의 값을 가지며 커패시턴스 값이 0.18 nF 미만으로 낮고, 약 3.3 이상의 유전율 및 66 % 이상의 유전유지율을 보여 안정성이 우수하고, 열저항이 낮고 열전도도가 높아 배터리 작동 시 발생하는 열기를 원활하게 배출할 수 있으며, 각각 73 또는 75 의 낮은 쇼어 00 경도를 가지는 것을 확인할 수 있다. Referring to Table 1, in the case of Examples 1 and 2, the surface resistance is high, the insulation property is 5800 kΩ or more, the capacitance value is as low as less than 0.18 nF, and the dielectric constant is about 3.3 or more and the dielectric retention is 66% or more. It has excellent stability, low thermal resistance and high thermal conductivity, so it can smoothly discharge heat generated during battery operation, and it can be seen that it has a low Shore 00 hardness of 73 or 75, respectively.
반면에 비교예 1의 경우 표면저항이 매우 낮고 절연특성이 열등하며, 커패시턴스 값이 0.260 nF로 너무 크고 유전율이 높으며 유전유지율이 낮아 전기차 배터리팩에 적용되는 경우 감전의 위험이 있을 수 있다. 즉, 비교예 1에서 제조한 열전도성 시트의 경우 절연 특성이 열등하고, 전기차 배터리팩에 적용되는 경우 안정성이 열등할 수 있다. On the other hand, in the case of Comparative Example 1, the surface resistance is very low, the insulation properties are inferior, the capacitance value is too large at 0.260 nF, the dielectric constant is high, and the dielectric retention rate is low, so when applied to an electric vehicle battery pack, there may be a risk of electric shock. That is, in the case of the thermal conductive sheet prepared in Comparative Example 1, insulation properties are inferior, and when applied to an electric vehicle battery pack, stability may be inferior.
비교예 2의 경우 열저항이 매우 높으며 열전도도가 매우 낮은 것을 확인할 수 있고, 이에 따라 열기 배출이 어려워 배터리가 과열되고 폭발 및 오작동 가능성이 상승할 수 있으며, 쇼어 00 경도가 85 로 높아, 롤 형태의 권취가 어려우므로 취급이 용이하지 않다. In the case of Comparative Example 2, it can be seen that the thermal resistance is very high and the thermal conductivity is very low. Accordingly, it is difficult to discharge heat, and the battery may overheat and the possibility of explosion and malfunction may increase. Handling is not easy because winding is difficult.
상기 결과를 종합하면, 본 발명의 일 구현예에 따른 열전도성 시트는 열전도성 및 절연 특성이 우수하고 적절한 수준의 경도를 가져 취급이 우수하나, 비교예 1과 같이 아크릴산을 포함하지 않는 열전도성 시트용 조성물을 이용하는 경우 절연특성이 매우 열등하고, 비교예 2와 같이 과량의 아크릴산을 포함하는 열전도성 시트용 조성물을 이용하는 경우 열전도성이 매우 열등하고 경도가 높아 본 발명의 효과를 달성할 수 없는 것을 확인할 수 있다. Summarizing the above results, the thermal conductive sheet according to one embodiment of the present invention has excellent thermal conductivity and insulation properties, has an appropriate level of hardness, and is excellent in handling, but does not contain acrylic acid as in Comparative Example 1. In the case of using the composition for thermal conductivity, the insulating properties are very inferior, and in the case of using the composition for thermal conductive sheet containing an excessive amount of acrylic acid as in Comparative Example 2, the thermal conductivity is very inferior and the hardness is high, so that the effect of the present invention cannot be achieved. You can check.
Claims (13)
A composition for a thermally conductive sheet comprising a thermally conductive filler, a plasticizer, acrylic acid and an alkyl (meth)acrylate monomer, wherein the acrylic acid is contained in an amount of 0.3 to 0.5 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate monomer A composition for thermally conductive sheets.
상기 열전도성 충전제는 수산화알루미늄, 산화 알루미늄, 질화 붕소, 질화 알루미늄, 산화 마그네슘, 수산화 마그네슘, 탄산 마그네슘, 산화 티탄, 산화 아연, 탄화 규소 또는 석영 중 1종 이상인 열전도성 시트용 조성물.
According to claim 1,
The thermally conductive filler is at least one of aluminum hydroxide, aluminum oxide, boron nitride, aluminum nitride, magnesium oxide, magnesium hydroxide, magnesium carbonate, titanium oxide, zinc oxide, silicon carbide, or quartz.
상기 열전도성 충전제는 상기 알킬 (메타)아크릴레이트 단량체 100 중량부에 대하여 500 중량부 내지 1000 중량부로 포함되는 열전도성 시트용 조성물.
According to claim 1,
The thermally conductive filler is included in 500 parts by weight to 1000 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate monomer.
상기 가소제는 점도가 10 cp 내지 450 cp인 열전도성 시트용 조성물.
According to claim 1,
The plasticizer is a composition for a thermally conductive sheet having a viscosity of 10 cp to 450 cp.
상기 가소제는 트리에틸헥실 트리멜리테이트, 트리이소노닐 트리멜리테이트또는 디이소노닐 아디페이트 중 1종 이상인 열전도성 시트용 조성물.
According to claim 1,
Wherein the plasticizer is at least one of triethylhexyl trimellitate, triisononyl trimellitate, and diisononyl adipate.
상기 가소제는 비점이 200 ℃ 내지 450 ℃인 열전도성 시트용 조성물.
According to claim 1,
The plasticizer has a boiling point of 200 ℃ to 450 ℃ composition for a thermally conductive sheet.
상기 가소제는 상기 알킬 (메타)아크릴레이트 단량체 100 중량부에 대하여 30 중량부 내지 80 중량부로 포함되는 열전도성 시트용 조성물.
According to claim 1,
The plasticizer is a composition for a thermally conductive sheet included in 30 parts by weight to 80 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate monomer.
상기 알킬 (메타)아크릴레이트 단량체는 탄소수 1 내지 15인 알킬 (메타)아크릴레이트를 포함하는 열전도성 시트용 조성물.
According to claim 1,
The alkyl (meth) acrylate monomer is a thermally conductive sheet composition comprising an alkyl (meth) acrylate having 1 to 15 carbon atoms.
상기 알킬 (메타)아크릴레이트 단량체는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, 프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 네오펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소노닐(메타)아크릴레이트, 라우릴(메타)아크릴레이트 또는 테트라데실(메타)아크릴레이트 중 1종 이상을 포함하는 열전도성 시트용 조성물.
According to claim 1,
The alkyl (meth) acrylate monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) Acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate A composition for a thermally conductive sheet comprising at least one of acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate.
광개시제 및 광경화제를 더 포함하는 열전도성 시트용 조성물.
According to claim 1,
A composition for a thermally conductive sheet further comprising a photoinitiator and a photocuring agent.
A thermally conductive sheet comprising a cured product of the composition for a thermally conductive sheet according to any one of claims 1 to 10, and having a surface resistance of 2*10 13 Ω/□ to 6*10 13 Ω/□.
쇼어 00 경도가 70 내지 80 인 열전도성 시트.
According to claim 11,
A thermally conductive sheet having a Shore 00 hardness of 70 to 80.
두께가 1.0 mm 내지 3.0 mm인 열전도성 시트.
According to claim 11,
A thermally conductive sheet having a thickness of 1.0 mm to 3.0 mm.
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| KR1020190082964A KR102476584B1 (en) | 2019-07-10 | 2019-07-10 | Composition for thermally conductive sheet and thermally conductive sheet prepared therefrom |
| EP20837521.2A EP3862369B1 (en) | 2019-07-10 | 2020-07-09 | Composition and heat dissipation sheet manufactured therefrom |
| PCT/KR2020/008976 WO2021006646A1 (en) | 2019-07-10 | 2020-07-09 | Composition and heat dissipation sheet manufactured therefrom |
| US17/282,562 US12012490B2 (en) | 2019-07-10 | 2020-07-09 | Composition and heat radiation sheet manufactured therefrom |
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| EP (1) | EP3862369B1 (en) |
| KR (1) | KR102476584B1 (en) |
| CN (1) | CN112839971B (en) |
| WO (1) | WO2021006646A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4067424A1 (en) | 2021-03-29 | 2022-10-05 | Omya International AG | Thermally conductive fillers |
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| JP2006160830A (en) | 2004-12-03 | 2006-06-22 | Three M Innovative Properties Co | Thermal conductive sheet and method for producing the same |
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| JP2008163126A (en) | 2006-12-27 | 2008-07-17 | Nippon Shokubai Co Ltd | Resin composition for heat-release material |
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| DE102008049849A1 (en) * | 2008-10-01 | 2010-04-08 | Tesa Se | Thermal conduction composition |
| JP5646812B2 (en) * | 2008-12-15 | 2014-12-24 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic heat conductive sheet and method for producing the same |
| CN102321444B (en) * | 2011-05-30 | 2012-11-07 | 天津安品有机硅材料有限公司 | Heat-conducting acrylic pressure-sensitive adhesive composition and acrylic heat-conducting patch |
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| JP6212950B2 (en) * | 2013-05-22 | 2017-10-18 | デクセリアルズ株式会社 | Photocurable acrylic heat conductive composition, acrylic heat conductive sheet and method for producing the same |
| DE102014207364A1 (en) * | 2014-04-16 | 2015-10-22 | Tesa Se | Adhesives, UV-crosslinkable PSAs and adhesives with UV-crosslinked PSAs |
| JP2020504802A (en) | 2016-11-30 | 2020-02-13 | ザ コカ・コーラ カンパニーＴｈｅ Ｃｏｃａ‐Ｃｏｌａ Ｃｏｍｐａｎｙ | On-demand processing of chilled food |
| CN108003818A (en) * | 2017-12-14 | 2018-05-08 | 深圳市德镒盟电子有限公司 | Low halogen fire retardant pressure sensitive glue of a kind of heat conduction and preparation method thereof |
| EP3727856A4 (en) * | 2017-12-21 | 2021-09-08 | 3M Innovative Properties Company | Multi-layered thermally conductive sheet |
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- 2019-07-10 KR KR1020190082964A patent/KR102476584B1/en active IP Right Grant
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2020
- 2020-07-09 CN CN202080005643.9A patent/CN112839971B/en active Active
- 2020-07-09 WO PCT/KR2020/008976 patent/WO2021006646A1/en unknown
- 2020-07-09 EP EP20837521.2A patent/EP3862369B1/en active Active
- 2020-07-09 US US17/282,562 patent/US12012490B2/en active Active
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| JP2006160830A (en) | 2004-12-03 | 2006-06-22 | Three M Innovative Properties Co | Thermal conductive sheet and method for producing the same |
| JP2007056067A (en) | 2005-08-22 | 2007-03-08 | Denki Kagaku Kogyo Kk | Electroinsulating flame retardant heat conductive material and heat conductive sheet using the same |
| KR101056694B1 (en) * | 2006-09-13 | 2011-08-12 | 주식회사 엘지화학 | Thermally Conductive Adhesive Composition |
| JP2008163126A (en) | 2006-12-27 | 2008-07-17 | Nippon Shokubai Co Ltd | Resin composition for heat-release material |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN112839971A (en) | 2021-05-25 |
| US12012490B2 (en) | 2024-06-18 |
| EP3862369B1 (en) | 2023-08-30 |
| WO2021006646A1 (en) | 2021-01-14 |
| EP3862369A4 (en) | 2021-11-24 |
| CN112839971B (en) | 2023-05-30 |
| EP3862369A1 (en) | 2021-08-11 |
| US20210340342A1 (en) | 2021-11-04 |
| KR20210008184A (en) | 2021-01-21 |
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